2-Thienyl azo dyestuff compounds

ABSTRACT

Azo compounds having the formula ##STR1## in which R 1  is cyano, aryl, an acyl radical or a carbamoyl radical, R 2  is hydrogen, alkyl, alkoxy, aralkyl or aryl, R 3  is alkyl, halogen, thiocyanato, arylazo or one of the substituents which R 1  can represent, and A is an aniline, tetrahydroquinoline, benzomorpholine or α-naphthylamine disperse azo dye coupling component. The azo compounds produce red to blue shades on polyamide, polyester and cellulose acetate fibers and exhibit improved fastness and dyeability properties on synthetic polyamide fibers.

This invention concerns certain novel azo compounds and polyamide textile materials dyed therewith. More particularly, this invention concerns monoazo disperse dyes containing novel thiophene diazo components.

Our novel compounds have the general formula ##STR2## wherein R¹ is cyano, aryl, lower alkanoyl, aroyl, lower alkoxycarbonyl, lower hydroxyalkoxycarbonyl, lower alkoxy-lower-alkoxycarbonyl, or the group --CONR⁴ R⁵

in which R⁴ individually is hydrogen, lower alkyl, cyclohexyl, lower alkylcyclohexyl, cyclohexylmethyl, lower alkylcyclohexylmethyl, lower hydroxyalkylcyclohexylmethyl, aryl-lower-alkyl, or aryl; R⁵ individually is hydrogen or lower alkyl; and R⁴ and R⁵ in combination are pentamethylene or ethyleneoxyethylene;

R² is hydrogen, lower alkyl, lower alkoxy, aryl-lower-alkyl or aryl;

R³ is lower alkyl, halogen, thiocyanato, arylazo, or a group which R¹ can represent;

A is an aniline, 1,2,3,4-tetrahydroquinoline, benzomorpholine or α-naphthylamine disperse azo dye coupling component;

in which each aryl moiety is phenyl or phenyl subsituted with lower alkyl, lower alkoxy, halogen, lower alkanoylamino, cyano or lower alkoxycarbonyl.

The azo compounds of the invention produce red to blue shades on polyamide, polyester and cellulose acetate fibers, yarns and fabrics when applied thereto according to conventional disperse dyeing procedures. Our azo compounds are especially valuable for dyeing synthetic polyamide fibers on which the compounds exhibit good to excellent dyeability and fastness properties, such as fastness to light and washing. The good dyeability of our compounds is manifested by the level shades they produce on synthetic polyamide fibers and their ability to build, i.e., produce significantly heavier shades as increased amounts of dye are applied to a given weight of undyed fibers. This desirable combination of properties which our azo compounds exhibit renders them especially valuable for dyeing carpets made from synthetic polyamide fibers and distinguishes them from known azo compounds containing a thiophene diazo component.

The substituents represented by R¹, R² and R³ are well known in the art and can be derived from known intermediates by published procedures. Examples of these substituents are contained in the detailed description of the couplers represented by A and in the examples. It is generally preferred that the substituents which R³ can represent are selected from the group consisting of aryl, cyano, lower alkanoyl, aroyl, lower alkoxycarbonyl, or the group --CONHR⁴. Particularly preferred thienyl diazo components are those in which R¹ is lower alkoxycarbonyl, carbamoyl or lower alkylcarbamoyl, R² is hydrogen, lower alkyl, or aryl, and R³ is aryl, aroyl, lower alkanoyl or lower alkoxycarbonyl, in which each aryl group is phenyl, tolyl or anisyl.

The coupler radicals represented by A are well known in the art of disperse azo dyes as evidenced by the great number of U.S. and foreign patents disclosing such radicals. These known coupling components are attached to the azo group by a carbon atom which is a ring member of the benzene moiety of the coupler and which is in a para-position relative to the nitrogen atom of the coupler nucleus.

The coupling components represented by A are further illustrated by the formulas ##STR3## in which R⁶ through R¹⁰ can represent hydrogen or a wide variety of substituents. Examples of the substituents represented by R⁶ and R⁷ include halogen and unsubstituted and substituted alkyl, alkoxy, alkylthio, arylthio and acylamido radicals. Such acylamido groups include those having the formula --NH--X--R¹³ in which X is --CO--, --COO--, or --SO₂ -- and R¹³ is unsubstituted or substituted alkyl, cycloalkyl, or aryl or when X is --CO--, R¹³ also can be amino, alkylamino, dialkylamino, arylamino, or furyl. The alkyl groups represented by R¹³ preferably are unsubstituted lower alkyl or lower alkyl substituted, for example, with halogen, aryl, cyano, lower alkylsulfonyl, hydroxy, lower alkylthio, lower alkanoyloxy, etc. As used herein to describe a substituent containing an alkyl moiety, "lower" designates a carbon content of one to about four carbon atoms. Cyclohexyl and lower alkylcyclohexyl are representative cycloalkyl groups represented by R¹³. Methylamino, ethylamino, and butylamino are typical alkylamino groups which R¹³ can represent. Typical aryl groups represented by R¹³ and the aryl component of the arylamino groups represented by R¹³ are described hereinbelow. Acetyl, propionyl, butyryl, cyanoacetyl, chloroacetyl, bromoacetyl, trifluoroacetyl, phenylacetyl, methoxyacetyl, ethylthioacetyl, methylsulfonylacetyl, methoxycarbonyl, propoxycarbonyl, butoxycarbonyl, methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, 2-cyanoethylsulfonyl, 2-methoxyethylsulfonyl, 2-chloroethylsulfonyl, cyclohexoyl, 4-ethylcyclohexoyl, benzoyl, 4-ethylbenzoyl, 4-cyanobenzoyl, 4-ethoxycarbonylbenzoyl, phenoxycarbonyl, 2,4-dichlorophenoxycarbonyl, 4-bromophenoxycarbonyl, 4-acetamidophenoxycarbonyl, benzenesulfonyl, p-toluenesulfonyl, 4-propionamidophenylsulfonyl, 4-chlorophenylsulfonyl, cyclohexoxycarbonyl, 4-butylcyclohexylsulfonyl, ethylcarbamoyl, butylsulfamoyl, phenylcarbamoyl, p-tolylcarbamoyl, p-anisylcarbamoyl, and phenylsulfamoyl are typical groups represented by --X--R¹³.

The alkyl and alkoxy groups which can be present on the coupler ring preferably are unsubstituted lower alkyl and lower alkoxy such as methyl, ethyl, methoxy, ethoxy and butoxy. Phenoxy, p-tolyloxy, p-ethoxyphenoxy, methylthio, ethylthio, butylthio, phenylthio, m-acetamidophenylthio, and p-chlorophenylthio are typical aryloxy, alkylthio and arylthio groups which can be present on the coupler ring. When R⁶ and R⁷ both represent substituents on the aniline-coupler, it is generally preferred that they be in a para relationship with each other.

R⁸ can represent unsubstituted or substituted alkyl of up to about eight or more carbon atoms, cycloalkyl such as the cycloalkyl groups represented by R¹³, or aryl. The substituents which can be present on alkyl radical R⁸ are limited primarily only by economic considerations and include hydroxy, lower alkoxy, halogen, cyano, succinimido, glutarimido, phthalimido, cyclohexyl, aryl, and groups having the formula --NH--X--R¹³, --X--R¹³, --OCO--R¹³, --OCOO--R¹³, --CONR⁴ R⁵ and --SO₂ NR⁴ R⁵. Couplers containing such substituents are well known in the art and/or can be prepared by known means. Preferably, the substituted alkyl radicals represented by R⁸ are substituted lower alkyl.

In addition to hydrogen, R⁹ can represent one of the unsubstituted or substituted alkyl groups which R⁸ can represent. R⁸ and R⁹ also can represent a single, combined group which, with the nitrogen atom to which each is attached, forms a ring. Examples of such combined groups include pentamethylene, ethyleneoxyethylene, and ethylenesulfonylethylene.

R¹⁰, R¹¹ and R¹² can represent hydrogen or lower alkyl. In the tetrahydroquinoline coupling components, it is preferred that R¹⁰ is methyl or, when R¹¹ and R¹² each is hydrogen, R¹⁰ is lower alkyl, and R¹¹ and R¹² each is hydrogen or methyl.

Preferred coupling components represented by A are the aniline and tetrahydroquinoline radicals having the formulas ##STR4## wherein R⁶ is hydrogen, lower alkyl, lower alkoxy, halogen, lower alkanoylamino, lower alkoxycarbonylamino, or benzamido;

R⁷ is hydrogen, lower alkoxy, or when R⁹ is hydrogen, R⁷ is lower alkyl;

R⁸ individually is lower alkyl; lower alkyl substituted with hydroxy, lower alkoxy, cyano, carbamoyl, lower alkylcarbamoyl, lower dialkylcarbamoyl, lower alkanoylamino, lower alkoxycarbonylamino, lower alkanoyloxy, 2-pyrrolidinono, or lower alkoxycarbonyl; or cyclohexyl;

R⁹ individually is hydrogen, lower alkyl, or lower alkyl substituted with hydroxy, lower alkoxy, lower alkanoyloxy, or lower alkoxycarbonyl;

R⁸ and R⁹ in combination are pentamethylene or ethyleneoxyethylene;

R¹¹ and R¹² are hydrogen or methyl.

The compounds of our invention which are especially valuable polyamide dyes because of their cost and performance, including shade, dyeability and fastness properties, on polyamide fibers are those designated below as Groups A, B and C. ##STR5## in which R¹ is lower alkoxycarbonyl, carbamoyl or lower alkylcarbamoyl, R⁶ is hydrogen, methyl, lower alkanoylamino or lower alkoxycarbonylamino, R⁷ is hydrogen or, when R⁹ is hydrogen, R⁷ is methyl, R⁸ is lower alkyl, hydroxyethyl, hydroxypropyl, lower alkanoyloxyethyl, lower alkanoyloxypropyl, carbamoylethyl, lower alkylcarbamoylethyl, lower alkanoylaminoethyl, lower alkanoylaminopropyl, lower alkoxycarbonylaminoethyl or lower alkoxycarbonylaminopropyl, and R⁹ is hydrogen, lower alkyl, hydroxyethyl, hydroxypropyl, lower alkanoyloxyethyl or lower alkanoyloxypropyl. ##STR6## in which R¹ and R³ each is lower alkoxycarbonyl, R² is hydrogen, methyl, or phenyl, and R⁶ through R⁹ are as defined in Group A. ##STR7## in which R¹ is lower alkoxycarbonyl, carbamoyl or lower alkylcarbamoyl and R⁶ through R⁹ are as defined in Group A.

Our novel compounds are synthesized by diazotizing an amine having the formula ##STR8## and coupling the resulting diazonium salt with a disperse dye coupler having the formula H--A. The amine diazo precursors are prepared according to procedures well documented in the literature: Z Chem., Volume 2, page 305 (1962); Chem, Ber., Volume 98, page 3571 (1965) and Volume 99, page 2712 (1966); and Chem. Heterocyclic Compds., Volume 2, page 285 (1966); and Volume 3, page 178 (1967). For example, an aldehyde or ketone having an unsubstituted or substituted α-methyl group can be condensed with an active cyanomethylene compound and elemental sulfur in the presence of a secondary amine. A second technique involves treating an activated vinyl compound bearing an unsubstituted or substituted β-methyl group with elemental sulfur in the presence of a secondary aliphatic amine. These reactions may be diagrammed as follows: ##STR9## Amines obtained by the above procedures can be modified, for example, by bromination followed by nucleophilic displacement reactions.

The novel compounds of the invention, their use and their preparation are further illustrated by the following examples.

EXAMPLE 1

To an ice cold nitrosylsulfuric acid solution, prepared by adding 0.72 g. of NaNO₂ to 5.0 ml. of 96% H₂ SO₄ below 80° C. followed by the addition of 10 ml. of 1:5 acid (1 part propionic acid and 5 parts acetic acid) below 20° C. is added slowly 2.18 g. of 2-amino-5-phenyl-3-thiophenecarboxamide. When the diazotization is complete, the diazonium solution is added with stirring to an ice cold solution of 2.63 g. of N-ethyl-N-2-acetamidoethyl-m-acetamidoaniline and 15 ml. of 1:5 acid. The coupling mixture is neutralized to Congo Red paper with the addition of ammonium acetate and is allowed to couple for 45 minutes. The azo product is precipitated by drowning in water and is collected by filtration, washed with water and air-dried. Recrystallization from 2-methoxyethanol gives an azo compound which dyes polyamide fibers blue-violet shades and displays good fastness properties.

The azo compounds described in the examples of Tables I, II, III and IV conform, respectively, to the general formula ##STR10## and are prepared according to the procedures described hereinabove. Example 1 of Table I designates the structure of the azo compound of preceding Example 1. The color given for each compound designates the shade produced by the compound on nylon fibers.

                                      TABLE I                                      __________________________________________________________________________     Ex.                                                                            No.                                                                               R.sup.1, R.sup.2, R.sup.3                                                                           R.sup.6, R.sup.7                                                                             Color                                    __________________________________________________________________________     1  3-CONH.sub.2 -5-C.sub.6 H.sub.5                                                                     3-NHCOCH.sub.3                                                                               Blue-Violet                              2  3-COOC.sub.2 H.sub.5 -4-CH.sub.3 5-COCH.sub.3                                                       3-CH.sub.3    Violet                                   3  3-COOC.sub.2 H.sub.5 -5-CH.sub.3                                                                    H             Red                                      4  3-COOC.sub.2 H.sub.5 -4-C.sub.6 H.sub.4 -p-OCH.sub.3 -5-Br                                          H             Violet                                   5  3-COOC.sub.2 H.sub.5 -4-C.sub.6 H.sub.4 -p-Cl-5-Cl                                                  H             Violet                                   6  3-COOCH.sub.2 CH.sub.2 CH.sub.3 -4,5-di-CH.sub.3                                                    H             Red                                      7  3-COOCH.sub.2 CH.sub.2 CH.sub.3 -4-CH.sub.3 -5-C.sub.2 H.sub.5                                      H             Red                                      8  3-COO(CH.sub.2).sub.3 CH.sub.3 -4,5-di-CH.sub.3                                                     H             Red                                      9  3-COO(CH.sub.2).sub.3 CH.sub.3 -4-CH.sub.3 -5-SCN                                                   H             Red                                      10 3-CN-5-N-N-C.sub.6 H.sub.5                                                                          H             Blue-Violet                              11 3-CN-4-C.sub.6 H.sub.5 -5-CH.sub.3                                                                  H             Red                                      12 3-COOCH.sub.2 CH.sub.2 OH-4-C.sub.6 H.sub.5 -5-CH.sub.3                                             3-CH.sub.3    Red                                      13 3-COOCH.sub.3 -4-CH.sub.3 -5-COCH.sub.3                                                             3-CH.sub.3    Violet                                   14 3-COOCH(CH.sub.3).sub.2 -4-CH.sub.3 -5-COCH.sub.3                                                   3-CH.sub.3    Violet                                   15 3-COOC.sub.2 H.sub.5 -5-C.sub.6 H.sub.5                                                             3-NHCOCH.sub.3                                                                               Blue-Violet                              16 3-COOC.sub.2 H.sub.5 -5-C.sub.6 H.sub.5                                                             3-NHCOCH.sub.3                                                                               Blue-Violet                              17 3-CONH.sub.2 -5-C.sub.6 H.sub.5                                                                     3-NHCOCH.sub.3                                                                               Blue                                     18 3-CONH.sub.2 -5-C.sub.6 H.sub.5                                                                     3-NHCOOCH.sub.3                                                                              Blue                                     19 3-CONH.sub.2 -5-C.sub.6 H.sub.5                                                                     3-NHCOCH.sub.2 OH                                                                            Blue-Violet                              20 3-CONHC.sub.2 H.sub.5 -5-C.sub.6 H.sub.5                                                            3-NHCOCH.sub.2 OOCCH.sub.3                                                                   Violet                                   21 3-CONHCH(CH.sub.3).sub.2 -5-C.sub.6 H.sub.5                                                         3-NHCOCH.sub.2 CN                                                                            Violet                                   22 3-CONH(CH.sub.2).sub.4 CH.sub.3 -5-C.sub.6 H.sub.5                                                  3-NHCOCH.sub.2 CONH.sub.2                                                                    Blue-Violet                              23 3-CON(C.sub.2 H.sub.5)-5-C.sub.6 H.sub.5                                                            3-NHCOC.sub.6 H.sub.5                                                                        Violet                                   24 3-CONHCH.sub.2 C.sub.6 H.sub.5 -5-C.sub.6 H.sub.5                                                   3-NHCOC.sub.6 H.sub.11                                                                       Blue-Violet                              25 3-CONH.sub.2 -5-C.sub.6 H.sub.4 -p-OCH.sub.3                                                        3-NHCOC.sub.2 H.sub.5                                                                        Blue-Violet                              26 3-CONH.sub.2 -5-C.sub.6 H.sub.4 -p-CH.sub.3                                                         2,5-di-Cl     Red-Violet                               27 3-CONH.sub.2 -5-C.sub.6 H.sub.4-m-Cl                                                                2-CH.sub.3 -5-OCH.sub.3                                                                      Violet                                   28 3-CONH.sub.2 -5-C.sub.6 H.sub.4 p-CN                                                                2-OCH.sub.3 -5-NHCOCH.sub.3                                                                  Blue                                     29 3-CONH.sub.2 -5-CH.sub.3                                                                            2-CH.sub.3    Red-Orange                               30 3-CONH.sub.2 -4,5-di-CH.sub.3                                                                       2-Cl          Orange                                   31 3-CONH.sub.2 -4-C.sub.6 H.sub.5 -5-CH.sub.3                                                         2-OCH.sub.3   Red                                      32 3-CN-4-CH.sub.3 -5-C.sub.6 H.sub.5                                                                  3-OCH.sub.3   Violet                                   33 3-COOC.sub.2 H.sub.5 -4-CH.sub.3 -5-C.sub.6 H.sub.5                                                 3-Cl          Violet                                   34 3-COOC.sub.2 H.sub.5 -4-CH.sub.3 -5-CONHC.sub.6 H.sub.4 -o-OCH.sub.3                                2,5-di-OCH.sub.3                                                                             Blue-Violet                              35 3-COOC.sub.2 H.sub.5 -4-CH.sub.3 -5-CONHC.sub.6 H.sub.4 -p-Cl                                       2,5-di-OCH.sub.3                                                                             Blue-Violet                              36 3-COOC.sub.2 H.sub.5 -4-CH.sub.3 -5-CONHC.sub.6 H.sub.4 -p-CH.sub.3                                 2,5-di-OCH.sub.3                                                                             Blue-Violet                              37 3-COOC.sub.2 H.sub.5 -5-COCH.sub.3                                                                  2,5-di-OCH.sub.3                                                                             Blue-Violet                              38 3-COOC.sub.2 H.sub.5 -COCH.sub.3                                                                    3-NHCOCH.sub.3                                                                               Blue-Violet                              39 3-COOC.sub.2 H.sub.5 -5-COCH.sub.3                                                                  3-NHCOCH.sub.3                                                                               Blue-Violet                              40 3-COOC.sub.2 H.sub.5 -5-COCH.sub.3                                                                  3-NHCOCH.sub.3                                                                               Violet                                   41 3-COOC.sub.2 H.sub.5 -5-COCH.sub.3                                                                  3-NHCOCH.sub.3                                                                               Violet                                   42 3,5-di-CN-4-CH.sub.3 2-CH.sub.3 -5-NHCOCH.sub.3                                                                   Blue-Violet                              43 3,5-di-CN-4-CH.sub.3 2-CH.sub.3 -5-NHCOCH.sub.3                                                                   Blue                                     44 3-CN-4-CH.sub.3 -5-CONHC.sub.6 H.sub.5                                                              2-CH.sub.3 -5-NHCOCH.sub.3                                                                   Blue                                     45 3-COOCH.sub.3 -4-CH.sub.3 -5-SCN                                                                    2-CH.sub.3 -5-NHCOOC.sub.2 H.sub.5                                                           Violet                                   46 3-COOCH.sub.3 -4-CH.sub.3 -5-CONHC.sub.6 H.sub.11                                                   2-OCH.sub.3 -5-NHCOCH.sub.3                                                                  Blue                                     47                                                                                 ##STR11##                                                                  48 3,5-di-CN-4-C.sub.6 H.sub.5                                                                         2-OCH.sub.3 -5-NHCOCH.sub.3                                                                  Blue-Violet                              49 3,5-di-COOC.sub.2 H.sub. 5 -4-CH.sub.3                                                              3-NHCOCH.sub.3                                                                               Violet                                   50 3,5-di-COOC.sub.2 H.sub.5 -4-CH.sub.3                                                               3-CH.sub.3    Red                                      51 3,5-di-COOC.sub.2 H.sub.5 -4-CH.sub.3                                                               H             Red                                      52 3,5-di-COOC.sub.2 H.sub.5 -4-CH.sub.3                                                               3-CH.sub.3    Violet                                   53 3,5-di-COOC.sub.2 H.sub.5 -4-CH.sub.3                                                               3-NHCOCH.sub.3                                                                               Violet                                   54 3-COOC.sub.2 H.sub.5 -5-COC.sub.6 H.sub.5                                                           3-NHCOCH.sub.3                                                                               Blue                                     55 3-COOC.sub.2 H.sub.5 -5-COC.sub.6 H.sub.5                                                           3-CH.sub.3    Blue-Violet                              56 3-CONH.sub.2 -5-C.sub.6 H.sub.5                                                                     3-CH.sub.3    Blue-Violet                              57 3-COHN.sub.2 -5-C.sub.6 H.sub.5                                                                     3-NHCOCH.sub.3                                                                               Blue-Violet                              58 3-CONH.sub.2 -5-C.sub.6 H.sub.5                                                                     H             Violet                                   59 3-CONHCH(CH.sub.3).sub.2 -5-C.sub.6 H.sub.5                                                         3-CH.sub.3    Blue-Violet                              60 3-CONHCH(CH.sub.3).sub.2 -5-C.sub.6 H.sub.5                                                         3-NHCOCH.sub.3                                                                               Blue                                     61 3-CONHCH(CH.sub.3).sub.2 -5-C.sub.6 H.sub.5                                                         H             Violet                                   62 3-CONH(CH.sub.2).sub.3 CH.sub.3 -5-C.sub.6 H.sub.5                                                  3-CH.sub.3    Blue-Violet                              63 3-CONH(CH.sub.2).sub.3 CH.sub.3 -5-C.sub.6 H.sub.5                                                  3-CH.sub.3    Blue-Violet                              64 3-CONH(CH.sub.2).sub.3 CH.sub.3 -5-C.sub.6 H.sub.5                                                  3-NHCOCH.sub.3                                                                               Blue                                     65 3-CONHC.sub.6 H.sub.5 -5-C.sub.6 H.sub.5                                                            3-CH.sub.3    Blue-Violet                              66 3-CONHC.sub.6 H.sub.5 -5-C.sub.6 H.sub.5                                                            3-CH.sub.3    Blue-Violet                              __________________________________________________________________________

                                      TABLE II                                     __________________________________________________________________________     Ex.                                                                            No.                                                                               R.sup.1, R.sup.2, R.sup.3                                                                     R.sup.6, R.sup.10, R.sup.11, R.sup.12                                                       R.sup.8        Color                            __________________________________________________________________________     67 3-CN-4-CH.sub.3 -5-Br                                                                         2,2,4-tri-CH.sub.3                                                                          CH.sub.2 CH.sub.2 CONH.sub.2                                                                  Violet                           68 3-COOC.sub.2 H.sub.5 -5-COC.sub.6 H.sub.5                                                     2,2,4-tri-CH.sub.3                                                                          CH.sub.2 CH.sub.2 NHCOCH.sub.2                                                                Blue                             69 3-CONH.sub.2 -4-CH.sub.3 -5-SCN                                                               2,2,4-tri-CH.sub.3                                                                          CH.sub.2 CH.sub.2 OH                                                                          Blue-Violet                      70 3-COOC.sub.2 H.sub.5 -4-CH.sub.3 -5-COC.sub.2 H.sub.5                                         2,2,4-tri-CH.sub.3                                                                          CH.sub.2 CH.sub.2 CN                                                                          Blue-Violet                      71 3-COOCH.sub.3 -5-C.sub.6 H.sub.5                                                              2-CH.sub.3 -7-NHCOCH.sub.3                                                                  C.sub.2 H.sub.5                                                                               Blue                             72 3-CONH.sub.2 -5-C.sub.6 H.sub.5                                                               2,2,4-tri-CH.sub.3 -7-NHCOCH.sub.3                                                          CH.sub.2 CH.sub.2 CONH.sub.2                                                                  Blue                             73 3-CONH.sub.2 -5-C.sub.6 H.sub.5                                                               2,2,4,7-tetra-CH.sub.3                                                                      C.sub.2 H.sub.5                                                                               Blue                             74 3-CONH.sub.2 -5-C.sub.6 H.sub.5                                                               2,2,4,7-tetra-CH.sub.3                                                                      CH.sub.2 CH.sub.2 Cl                                                                          Blue-Violet                      75 3-CONH.sub.2 -5-C.sub.6 H.sub.5                                                               2,2,4,7-tetra-CH.sub.3                                                                      CH.sub.2 CH.sub.2 OOCC.sub.2 H.sub.5                                                          Blue-Violet                      76 3-CONH.sub.2 -5-C.sub.6 H.sub.5                                                               2,2,4,7-tetra-CH.sub.3                                                                      CH.sub.2 CH.sub. 2 OC.sub.2 H.sub.5                                                           Blue                             77 3-CONH.sub.2 -5-C.sub.6 H.sub.5                                                               2,7-di-CH.sub.3                                                                             CH.sub.2 CH.sub.2 CONH.sub.2                                                                  Blue-Violet                      78 3-COOC.sub.2 H.sub.5 -5-C.sub.6 H.sub.5                                                       2,2,4,7-tetra-CH.sub.3                                                                      CH.sub.2 CH.sub.2 CONHC.sub.2 H.sub.5                                                         Blue                             79 3-COOC.sub.2 H.sub.5 -5-C.sub.6 H.sub.5                                                       2,2,4,7-tetra-CH.sub.3                                                                      CH.sub.2 CH.sub.2 CONH(CH.sub.2).sub.3                                         CH.sub.3       Blue                             80 3-COOC.sub.2 H.sub.5 -5-C.sub.6 H.sub.5                                                       2,2,4,7-tetra-CH.sub.3                                                                      CH.sub.2 CH.sub.2 CON(C.sub.2 H.sub.5).sub.                                    2              Blue                             81 3-CONH.sub.2 -5-C.sub.6 H.sub.5                                                               2,2,4,7-tetra-CH.sub.3                                                                      CH.sub.2 CH.sub.2 CONHCH.sub.2 C.sub.6                                         H.sub.5        Blue                             82 3-CONH.sub.2 -5-C.sub.6 H.sub.5                                                               2,2,4,7-tetra-CH.sub.3                                                                      CH.sub.2 CH.sub.2 OOCOC.sub.2 H.sub.5                                                         Blue                             83 3-CONHCH(CH.sub.3).sub.2 -5-C.sub.6 H.sub.5                                                   2,2,4,7-tetra-CH.sub.3                                                                      CH.sub.2 CH.sub.2 CONH.sub.2                                                                  Blue                             84 3-CONHCH(CH.sub.3).sub.2 -5-C.sub.6 H.sub.5                                                   2,2,4,7-tetra-CH.sub.3                                                                       ##STR12##     Blue                             85 3-COOC.sub.2 H.sub.5 -4-CH.sub.3 -5-COCH.sub.3                                                2-CH(CH.sub.3).sub.2 -7-NHCOCH.sub.3                                                        C.sub.2 H.sub.5                                                                               Blue                             86 3-COOC.sub.2 H.sub.5 -4-CH.sub.3 -5-COCH.sub.3                                                7-CH.sub.3   CH.sub.2 CH.sub.2 NHCOCH.sub.3                                                                Blue-Violet                      87 3-COOC.sub.2 H.sub.5 -4-CH.sub.3 -5-COCH.sub.3                                                2,7-di-CH.sub.3                                                                             CH.sub.2 CH.sub.2 CONH.sub.2                                                                  Blue-Violet                      88 3-COOC.sub.2 H.sub.5 -5-COCH.sub.3                                                            2-CH.sub.3   CH.sub.2 CH.sub.2 Br                                                                          Blue-Violet                      89 3-CONH.sub.2 -5-COCH.sub.3                                                                    H            CH.sub.2 CH.sub.2 NHCOCH.sub.2 OH                                                             Violet                           90 3-CONH.sub.2 -4-CH.sub.3 -COCH.sub.3                                                          H            CH.sub.2 CH.sub.2 COCHCH.sub.2                                                                Violet                           91 3,5-di-COOC.sub.2 H.sub.5 -4-CH.sub.3                                                         2,2,4,7-tetra-CH.sub.3                                                                      C.sub.2 H.sub.5                                                                               Violet                           92 3,5-di-COOC.sub.2 H.sub.5 -4-CH.sub.3                                                         2,2,4,7-tetra-CH.sub.3                                                                      CH.sub.2 CH.sub.2 NHCOCH.sub.3                                                                Violet                           93 3,5-di-COOC.sub.2 H.sub.5 -4-CH.sub.3                                                         2,2,4,7-tetra-CH.sub.3                                                                      CH.sub.2 CH.sub.2 OH                                                                          Violet                           94 3,5-di-COOC.sub.2 H.sub.5 -4-CH.sub.3                                                         2,2,4,7-tetra-CH.sub.3                                                                      CH.sub.2 CH.sub.2 OOCCH.sub.3                                                                 Violet                           95 3,5-di-COOC.sub.2 H.sub.5 -4-CH.sub.3                                                         2,2,4-tri-CH.sub.3 -7-NHCOCH.sub.3                                                          C.sub.2 H.sub.5                                                                               Blue-Violet                      96 3,5-di-COOC.sub.2 H.sub.5 -4-CH.sub.3                                                         2,2,4-tri-CH.sub.3 -7-NHCOCH.sub.3                                                          CH.sub.2 CH.sub.2 CONH.sub.2                                                                  Blue-Violet                      97 3,5-di-COOC.sub.2 H.sub.5 -4-CH.sub.3                                                         2,2,4-tri-CH.sub.3 -7-NHCOCH.sub.3                                                          CH.sub.2 CH.sub.2 OH                                                                          Blue-Violet                      98 3,5-di-COOC.sub.2 H.sub.5 -4-CH.sub.3                                                         2,2,4-tri-CH.sub.3 -7-NHCOCH.sub.3                                                          CH.sub.2 C.sub.6 H.sub.5                                                                      Blue-Violet                      __________________________________________________________________________

                                      TABLE III                                    __________________________________________________________________________     Ex.                                                                            No.                                                                               R.sub.1, R.sup.2, R.sup.3                                                                           R.sup.6, R.sup.10                                                                        R.sup.8       Color                          __________________________________________________________________________      99                                                                               3-COOC.sub.2 H.sub.5 -4-C.sub.6 H.sub.5 -5-Br                                                       2,7-di-CH.sub.3                                                                          --C.sub.2 H.sub.5                                                                            Violet                         100                                                                               3-COOC.sub.2 H.sub.5 -4-C.sub.6 H.sub.4 -p-OCH.sub.3 -5-SCN                                         2,7-di-CH.sub.3                                                                          --C.sub.2 H.sub.5                                                                            Violet                         101                                                                               3,5-di-COOC.sub.2 H.sub.5 -4-CH.sub.3                                                               2,7-di-CH.sub.3                                                                          --CH.sub.2 CH.sub.2 CH.sub.2 NHCOCH.sub.                                       3             Violet                         102                                                                               3,5-di-COOC.sub.2 H.sub.5 -4-CH.sub.3                                                               2,7-di-CH.sub.3                                                                          --CH.sub.2 CH.sub.2 OH                                                                       Violet                         103                                                                               3-COOC.sub.2 H.sub.5 -4-CH.sub.3 -5-COCH.sub.3                                                      2,7-di-CH.sub.3                                                                          --C.sub.2 H.sub.5                                                                            Blue-Violet                    104                                                                               3,5-di-COOC.sub.2 H.sub.5 -4-CH.sub.3                                                               2,7-di-CH.sub.3                                                                          --CH.sub.2 CH.sub.2 COOCH.sub.2 C.sub.6                                        H.sub.5       Violet                         105                                                                               3-CN-4-CH.sub.3 -5-CONHC.sub.6 H.sub.4 -p-OCH.sub.3                                                 2,7-di-CH.sub.3                                                                          --C.sub.2 H.sub.5                                                                            Violet                         106                                                                               3-CN-4-CH.sub.3 -5-CONHC.sub.6 H.sub.5                                                              2,7-di-CH.sub.3                                                                          --C.sub.2 H.sub.5                                                                            Violet                         107                                                                               3-CONH.sub.2 -5-C.sub.6 H.sub.5                                                                     2-CH.sub.3                                                                               --C.sub.2 H.sub.5                                                                            Violet                         108                                                                               3-CONH.sub.2 -4-CH.sub.3 -5-C.sub. 6 H.sub.5                                                        2-CH.sub.3                                                                               --C.sub.2 H.sub.5                                                                            Violet                         109                                                                               3-CONH.sub.2 -5-C.sub.6 H.sub.5                                                                     2-CH.sub.3                                                                               --CH.sub.2 CH(OH)CH.sub.2 OH                                                                 Violet                         110                                                                               3-CONH.sub.2 -5-CH.sub.3                                                                            2-CH.sub.3                                                                               --CH.sub.2 CH.sub.2 Cl                                                                       Red                            111                                                                               3-CONH.sub.2 -4,5-di-CH.sub.3                                                                       2-CH.sub.3                                                                               --CH.sub.2 CH.sub.2 CN                                                                       Red                            112                                                                               3-CONH.sub.2 -4,5-di-C.sub.6 H.sub.5                                                                2-CH.sub.3                                                                               --CH.sub.2 CH.sub.2 CONH.sub.2                                                               Red                            113                                                                               3-CONH.sub.2 -4-CH.sub.3 -5-COCH.sub.3                                                              2-CH.sub.3                                                                               --CH.sub.2 CH.sub.2 NHCOCH.sub.3                                                             Violet                         114                                                                               3-CONHCH.sub.2 CH.sub.2 CH.sub.3 -4-CH.sub.3 -5-C.sub.6 H.sub.5                                     2-CH.sub.3                                                                               --(CH.sub.2).sub.3 NHCOCH.sub.3                                                              Violet                         115                                                                               3-CONHCH.sub.2 CH.sub.2 CH.sub.3 -4-CH.sub.3 -5-C.sub.6 H.sub.5                                     2-CH.sub.3                                                                               --CH.sub.2 CH.sub.2 NHCOCNH.sub.2                                                            Violet                         116                                                                               3-CONH(CH.sub.2).sub.3 CH.sub.3 -5-C.sub.6 H.sub.5                                                  2,7-di-CH.sub.3                                                                          --C.sub.2 H.sub.5                                                                            Blue                           117                                                                               3-CONH(CH.sub.2).sub.3 CH.sub.3 -4-C.sub.6 H.sub.5 -5-CH.sub.3                                      2-CH.sub.3 -7-NHCOCH.sub.3                                                               --CH.sub.2 CH.sub.2 NHCOCH═CH.sub.2                                                      Blue-Violet                    118                                                                               3-CON(C.sub.2 H.sub.5).sub.2 -4-CH.sub.3 -5-C.sub.6 H.sub.5                                         2-CH.sub.3 -7-NHCOCH.sub.3                                                               --CH.sub.2 CH.sub. 2 NHCON(CH.sub.3).sub                                       .2            Violet                         119                                                                               3-CON(C.sub.2 H.sub.5).sub.2 -4-CH.sub.3 -5-CONHC.sub.6 H.sub.4                -p-CH.sub.3          2-CH.sub.3 -7-NHCOCH.sub.3                                                               --CH.sub.2 CH.sub.2 NHCOOC.sub.2                                               H.sub.5       Violet                         120                                                                               3-COOCH(CH.sub.3).sub.2 -4-CH.sub.3 -5-C.sub.6 H.sub.5                                              2-CH.sub.3 -7-NHCOCH.sub.3                                                               --CH.sub.2 CH.sub.2 NHSO.sub.2 CH.sub.3                                                      Blue-Violet                    __________________________________________________________________________

                                      TABLE IV                                     __________________________________________________________________________     Ex.                     Naphthalene                                            No.                                                                               R.sup.1, R.sup.2, R.sup.3                                                                           Substituents                                                                          R.sup.8         R.sup.9   Color                 __________________________________________________________________________     121                                                                               3-CONH.sub.2 -5-C.sub.6 H.sub.5                                                                     H      C.sub.6 H.sub.5 H         Blue                  122                                                                               3-COOC.sub.2 H.sub.5 -5-C.sub.6 H.sub.5                                                             H      C.sub.6 H.sub.5 H         Blue-Violet           123                                                                               3-COOC.sub.2 H.sub.5 -5-C.sub.6 H.sub.5                                                             5-OH   C.sub.6 H.sub.5 H         Blue                  124                                                                               3-CONH.sub.2 -5-C.sub.6 H.sub.5                                                                     H      C.sub.6 H.sub.11                                                                               H         Blue                  125                                                                               3-CONH.sub.2 -4-CH.sub.3 -5-C.sub.6 H.sub.5                                                         H      C.sub.2 H.sub.5 H         Blue-Violet           126                                                                               3-COOC.sub.2 H.sub.5 -4-CH.sub.3 -5-C.sub.6 H.sub.5                                                 2-OCH.sub.3                                                                           CH.sub.2 CH.sub.2 NHCOCH.sub.3                                                                 H         Blue                  127                                                                               3-COOC.sub.2 H.sub.5 -4,5-di-CH.sub.3                                                               H      CH.sub.2 CH.sub.2 COOC.sub.2 H.sub.5                                                           H         Violet                128                                                                               3-CONH.sub.2 -5-CH.sub.3                                                                            H      C.sub.6 H.sub.11                                                                               H         Violet                129                                                                               3-CN-5-CH.sub.3      H      C.sub.2 H.sub.5 C.sub.2 H.sub.5                                                                          Red                   130                                                                               3-CN-4-CH.sub.3 -5-SCN                                                                              H      CH.sub.2 CH.sub.2 OH                                                                           CH.sub.2                                                                                 Violet.2 CN           131                                                                               3,5-di-COOC.sub.2 H.sub.5 -4-CH.sub.3                                                               5-OH   CH.sub.2 CH.sub.2 OOCCH.sub.3                                                                  CH.sub.2 CH.sub.2 CN                                                                     Violet                132                                                                               3,5-di-COOC.sub.2 H.sub.5 -4-CH.sub.3                                                               5-OH   CH.sub.2 C.sub.6 H.sub.11                                                                      H         Blue-Violet           133                                                                               3,5-di-COOC.sub.2 H.sub.5 -4-CH.sub.3                                                               2-OCH.sub.3                                                                           CH.sub.2 C.sub.6 H.sub.11                                                                      H         Blue-Violet           134                                                                               3-CONH.sub.2 -4-CH.sub.3 -5-Br                                                                      5-OH   CH.sub.2 C.sub.6 H.sub.11                                                                      H         Blue-Violet           135                                                                               3,5-di-CN-4-CH.sub.3 H      CH.sub.2 C.sub.6 H.sub.11                                                                      CH.sub.2 C.sub.6 H.sub.11                                                                Blue-Violet           136                                                                               3-COOCH.sub.3 -4-CH.sub.3 -5-COCH.sub.3                                                             H      CH.sub.2 CH.sub.2 OH                                                                           CH.sub.2 CH.sub.2 OH                                                                     Blue-Violet           137                                                                               3-COOCH.sub.3 -5-COCH.sub.3                                                                         H      CH.sub.2 CH.sub.2 OH                                                                           CH.sub.2 CH.sub.2 CONH.sub.                                                    2         Blue-Violet           138                                                                               3-COOC.sub.2 H.sub.5 -5-COCH.sub.3                                                                  H      CH.sub.2 CH(OH)CH.sub.2 OH                                                                     H         Blue                  139                                                                               3-COOC.sub.2 H.sub.5 -4-CH.sub.3 -5-CONHC.sub.6 H.sub.4 -p-CH.sub.3                                 H      CH.sub.2 CH.sub.2 SO.sub.2 CHCH.sub.2                                                          H         Violet                140                                                                               3-COOC.sub.2 H.sub.5 -4-CH.sub.3 -5-CONHC.sub.6 H.sub.4 -p-Cl                                       H      CH.sub.2 CH.sub.2 SO.sub.2 CHCH.sub.                                                           H         Violet                141                                                                               3,5-di-CN-4-C.sub.6 H.sub.5                                                                         H      CH.sub.2 CH.sub.2 SO.sub.2 CHCH.sub.2                                                          H         Blue-Violet           142                                                                               3-CONH.sub.2 -4-C.sub.6 H.sub.5 -5-COOC.sub.2 H.sub.5                                               H      CH.sub.2 CH.sub.2 SO.sub.2 CHCH.sub.2                                                          H         Blue-Violet           143                                                                               3-CN-4-C.sub.6 H.sub.5 -5-Br                                                                        H      CH.sub.2 CH.sub.2 SO.sub.2 CHCH.sub.2                                                          H         Violet                144                                                                               3-CONH.sub.2 -5-C.sub.6 H.sub.5                                                                     H      C.sub.2 H.sub.5 H         Blue                  145                                                                               3-CONH.sub.2 -5-C.sub.6 H.sub.5                                                                     H      CH.sub.2 CH.sub.2 CONH.sub.2                                                                   H         Blue                  146                                                                               3-CONH.sub.2 -5-C.sub.6 H.sub.5                                                                     H      CH.sub.2 CH.sub.2 NHCOCH.sub.3                                                                 H         Blue                  147                                                                               3-CONH.sub.2 -5-C.sub.6 H.sub.5                                                                     H      (CH.sub.2).sub.3 NHCOCH.sub.3                                                                  H         Blue                  148                                                                               3-CONH.sub.2 -5-C.sub.6 H.sub.5                                                                     H                                                                                      ##STR13##      H         Blue                  149                                                                               3-CONHCH(CH.sub.3).sub.2 -5-C.sub.6 H.sub.5                                                         H      CH.sub.2 CH.sub.2 OH                                                                           H         Blue                  150                                                                               3-CONHCH(CH.sub.3).sub.2 -5-C.sub.6 H.sub.5                                                         H      (CH.sub.2).sub.3 OH                                                                            H         Blue                  151                                                                               3-CONHCH(CH.sub.3).sub.2 -5-C.sub.6 H.sub.5                                                         H      CH.sub.2 CH.sub.2 NHCOOC.sub.2 H.sub.5                                                         H         Blue                  152                                                                               3-CONHCH(CH.sub.3).sub.2 -5-C.sub.6 H.sub.5                                                         H      CH.sub.2 C.sub.6 H.sub.11                                                                      H         Blue                  153                                                                               3-CONHCH(CH.sub.3).sub.2 -5-C.sub.6 H.sub.5                                                         H      CH.sub.2 C.sub.6 H.sub.10 -p-CH.sub.2                                                          HH        Blue                  154                                                                               3-COOC.sub.2 H.sub.5 -5-C.sub.6 H.sub.5                                                             H      CH(CH.sub.3)C.sub.2 H.sub.5                                                                    H         Blue                  155                                                                               3-COOC.sub.2 H.sub.5 -5-C.sub.6 H.sub.5                                                             H      CH.sub.2 CH(OH)CH.sub.2 Cl                                                                     H         Blue                  156                                                                               3-COOC.sub.2 H.sub.5 -5-C.sub.6 H.sub.5                                                             H      CH.sub.2 CH(OH)CH.sub.2 OCH(CH.sub.3).sub.2                                                    H         Blue                  157                                                                               3-COOC.sub.2 H.sub.5 -5-C.sub.6 H.sub.5                                                             H      CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                           HH        Blue                  158                                                                               3-COOC.sub.2 H.sub.5 -5-C.sub.6 H.sub.5                                                             H      CH.sub.2 CH.sub.2 CN                                                                           H         Blue                  159                                                                               3-COOC.sub.2 H.sub.5 -5-COC.sub.6 H.sub.5                                                           H      CH.sub.2 CH.sub.2 CONHCH(CH.sub.3).sub.2                                                       H         Blue                  160                                                                               3-COOC.sub.2 H.sub.5 -5-COC.sub.6 H.sub.5                                                           H      CH.sub.2 CH.sub.2 COOC.sub.2 H.sub.5                                                           H         Blue                  161                                                                               3-COOC.sub.2 H.sub.5 -5-COC.sub.6 H.sub.5                                                           H      CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                           OCH.sub.3       H         Blue                  162                                                                               3-COOC.sub.2 H.sub.5 -5-COC.sub.6 H.sub.5                                                           H      (CH.sub.2).sub.6 NHCOCH.sub.3                                                                  H         Blue                  163                                                                               3-CONHC.sub.2 H.sub.5 -5-COC.sub.6 H.sub.5                                                          H      CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                              H         Blue                  164                                                                               3-CONHC.sub.2 H.sub.5 -5-COC.sub.6 H.sub.5                                                          H      CH.sub.2 C.sub.6 H.sub.4 -p-OCH.sub.3                                                          H         Blue                  165                                                                               3-CONHC.sub.2 H.sub.5 -5-COC.sub.6 H.sub.5                                                          H      CH.sub.2 CHCH.sub.2                                                                            H         Blue                  __________________________________________________________________________

The novel azo compounds can be applied to synthetic polyamide polyester and cellulose acetate fibers according to known disperse dyeing techniques. Various dispersing and wetting agents can be employed in the dispersion of the finely divided dye compound in an essentially aqueous dyebath. Procedures by which the compounds of the invention can be applied to polyamide textile materials are described in U.S. Pat. Nos. 3,100,134 and 3,320,021. The following example illustrates a method for applying the novel compounds to polyamide fibers.

EXAMPLE 166

The azo compound (16.7 mg.) of Example 1 is dispersed in 10 cc. of 2-methoxyethanol. A small amount (3-5 cc.) of a 3% sodium lignin sulfonate solution is added, with stirring, and then the volume of the bath is brought to 150 cc. with water. A 5 g. textile fabric made of nylon 66 fibers is placed in the bath and worked 10 minutes without heat. The bath is then slowly brought to the boil over a 30-minute period and the dyeing is carried out at the boil for one hour. The dyed fabric is then removed from the dyebath, rinsed with water and dried in an oven at 250° F. The fabric is dyed a bright shade of blue-violet exhibiting excellent fastness properties when tested in accordance with the procedures described in the Technical Manual of the American Association of Textile Chemists and Colorists, 1968 edition.

The synthetic polyamide fibers which can be dyed with the novel azo compounds are well known and have a basis of a linear polyamide such as nylon 66 (polyhexamethylene adipamide) manufactured by the polymerization of adipic acid and hexamethylenediamine, nylon 6 (polycaprolactum) prepared from epsilon-aminocaproic acid lactum (caprolactum) and nylon 8. A detailed description of the synthetic polyamide materials which are dyed bright, fast shades by the compounds of the invention is set forth in U.S. Pat. No. 3,100,134.

The invention has been described in considerable detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention. 

We claim:
 1. A compound having the formula ##STR14## wherein R¹ is cyano; lower alkanoyl; benzoyl and benzoyl substituted with lower alkyl or lower alkoxy of 1-6 carbons, chlorine and bromine; lower alkoxycarbonyl; lower hydroxyalkoxycarbonyl; lower alkoxy-lower-alkoxycarbonyl; or the group --CONR⁴ R⁵ in which R⁴ individually is hydrogen, lower alkyl, cyclohexyl, lower alkylcyclohexyl, cyclohexylmethylene, lower alkylcyclohexylmethylene, lower hydroxyalkylcyclohexylmethylene, or phenyl-lower-alkylene; R⁵ individually is hydrogen or lower alkyl; and R⁴ and R⁵ in combination are pentamethylene; R² is hydrogen, lower alkyl, lower alkoxy, aryl-lower-alkylene or aryl; R³ is aryl or a group which R¹ can represent; A is a disperse azo dye coupling component selected from an aniline having the formula ##STR15## wherein R⁶ is hydrogen, lower alkyl, lower alkoxy, chlorine, bromine, lower alkanoylamino, lower alkoxycarbonylamino, or ##STR16## R⁷ is hydrogen, lower alkoxy, or when R⁹ is hydrogen, R⁷ is lower alkyl; R⁸ individually is lower alkyl; lower alkyl substituted with hydroxy, lower alkoxy, cyano, carbamoyl, lower alkylcarbamoyl, lower dialkylcarbamoyl, lower alkanoylamino, lower alkoxycarbonylamino, lower alkanoyloxy, or lower alkoxycarbonyl; or cyclohexyl; R⁹ individually is hydrogen; lower alkyl; or lower alkyl substituted with hydroxy, lower alkoxy, lower alkanoyloxy or lower alkoxycarbonyl; and R⁸ and R⁹ in combination are pentamethylene or ethyleneoxyethylene; a 1,2,3,4-tetrahydroquinoline having the formula ##STR17## wherein R⁶ is as defined above; R⁸ is as defined above; and R¹¹ and R¹² are hydrogen or methyl; a benzomorpholine having the formula ##STR18## in which R⁶ and R⁸ are as defined above and R¹⁰ is hydrogen or lower alkyl; or an α-naphthylamine having the formula ##STR19## wherein R⁸ is as defined above; in which each aryl moiety is phenyl or phenyl substituted with lower alkyl, lower alkoxy, chlorine, bromine, lower alkanoylamino, cyano or lower alkoxycarbonyl.
 2. A compound according to claim 1 having the formula ##STR20## wherein R¹ is lower alkoxycarbonyl, carbamoyl, or lower alkylcarbamoyl;R² is hydrogen, lower alkyl or aryl; R³ is aryl, lower alkanoyl, benzoyl and benzoyl substituted with lower alkyl or lower alkoxy of 1-6 carbons, chlorine and bromine, or lower alkoxycarbonyl; R⁶ is hydrogen, lower alkyl, lower alkoxy, chlorine, bromine, lower alkanoylamino, lower alkoxycarbonylamino, or ##STR21## R⁷ is hydrogen, lower alkoxy, or when R⁹ is hydrogen, R⁷ is lower alkyl; R⁸ individually is lower alkyl; lower alkyl substituted with hydroxy, lower alkoxy, cyano, carbamoyl, lower alkylcarbamoyl, lower dialkylcarbamoyl, lower alkanoylamino, lower alkoxycarbonylamino, lower alkanoyloxy, or lower alkoxycarbonyl; or cyclohexyl; R⁹ individually is hydrogen, lower alkyl, or lower alkyl substituted with hydroxy, lower alkoxy, lower alkanoyloxy or lower alkoxycarbonyl; and R⁸ and R⁹ in combination are pentamethylene or ethyleneoxyethylene.
 3. A compound according to claim 1 having the formula ##STR22## wherein R¹ is lower alkoxycarbonyl, carbamoyl or lower alkylcarbamoyl;R⁶ is hydrogen, methyl, lower alkanoylamino or lower alkoxycarbonylamino; R⁷ is hydrogen or, when R⁹ is hydrogen, R⁷ is methyl; R⁸ is lower alkyl, hydroxyethyl, hydroxypropyl, lower alkanoyloxyethyl, lower alkanoyloxypropyl, carbamoylethyl, lower alkylcarbamoylethyl, lower alkanoylaminoethyl, lower alkanoylaminopropyl, lower alkoxycarbonylaminoethyl or lower alkoxycarbonylaminopropyl; and R⁹ is hydrogen, lower alkyl, hydroxyethyl, hydroxypropyl, lower alkanoyloxyethyl or lower alkanoyloxypropyl.
 4. A compound according to claim 1 having the formula ##STR23## wherein R¹ and R³ each is lower alkoxycarbonyl;R² is hydrogen, methyl or aryl; R⁶ is hydrogen, methyl, lower alkanoylamino or lower alkoxycarbonylamino; R⁷ is hydrogen, or, when R⁹ is hydrogen, R⁷ is methyl; R⁸ is lower alkyl, hydroxyethyl, hydroxypropyl, lower alkanoyloxyethyl, lower alkanoyloxypropyl, carbamoylethyl, lower alkylcarbamoylethyl, lower alkanoylaminoethyl, lower alkanoylaminopropyl, lower alkoxycarbonylaminoethyl or lower alkoxycarbonylaminopropyl; and R⁹ is hydrogen, lower alkyl, hydroxyethyl, hydroxypropyl, lower alkanoyloxyethyl or lower alkanoyloxypropyl.
 5. A compound according to claim 1 having the formula ##STR24## wherein R¹ is lower alkoxycarbonyl, carbamoyl or lower alkylcarbamoyl;R⁶ is hydrogen, methyl, lower alkanoylamino or lower alkoxycarbonylamino; R⁷ is hydrogen or, when R⁹ is hydrogen, R⁷ is methyl; R⁸ is lower alkyl, hydroxyethyl, hydroxypropyl, lower alkanoyloxyethyl, lower alkanoyloxypropyl, carbamoylethyl, lower alkylcarbamoylethyl, lower alkanoylaminoethyl, lower alkanoylaminopropyl, lower alkoxycarbonylaminoethyl or lower alkoxycarbonylaminopropyl; and R⁹ is hydrogen, lower alkyl, hydroxyethyl, hydroxypropyl, lower alkanoyloxyethyl or lower alkanoyloxypropyl.
 6. A compound of the formula ##STR25## wherein X is --CN; --COR; --CO-phenyl or --CO-phenyl substituted by --R, --OR, Cl or Br; --COOR--OH; --COOR; --COOR--OR; or --CONR₅ R₆ in which R₅ is individually H, --R, --C₆ H₁₁ --R, --R--C₆ H₁₁, --C₆ H₁₁, --R--C₆ H₁₁ --R, --R--C₆ H₁₁ --R--OH or --R-phenyl;R₆ is individually H or --R; and, R₅ and R₆ in combination are pentamethylene; Y is H, --R; --OR; phenyl or phenyl substituted by --R, --OR, Cl, Br, --NHCOR, --CN or --COOR; --R-phenyl or --R-phenyl substituted by --R, --OR, Cl, Br, --CN, --NHCOR or --COOR; Z is X, phenyl or phenyl substituted by --R, --OR, Cl, Br, --NHCOR, --CN or --COOR; R₁ is H, --R, --OR, Cl, Br, --NHCOR, --NHCOOR or --NHCO-phenyl; R₂ is H; --OR; or when R₄ is H, R₂ is --R; R₃ is --R, --R--OH, --R--OR, --R--CN, --R--CONH₂, --R--CONHR, --R--CON(R)₂, --R--NHCOR, --R--NHCOOR, --R--OCOR, --RCOOR or --R--C₆ H₁₁ ; R₄ is H, --R, --R--OH, --R--OR, --R--OCOR or --R--COOR; and R is alkyl or alkylene as the case may be.
 7. A compound according to claim 1 having the formula ##STR26##
 8. A compound according to claim 1 having the formula ##STR27##
 9. A compound according to claim 1 having the formula ##STR28##
 10. A compound according to claim 1 having the formula ##STR29##
 11. A compound according to claim 1 having the formula ##STR30##
 12. A compound according to claim 1 having the formula ##STR31##
 13. A compound according to claim 1 having the formula ##STR32## wherein R¹ is lower alkoxycarbonyl, carbamoyl, or lower alkylcarbamoyl;R² is hydrogen, lower alkyl or aryl; R³ is aryl, lower alkanoyl, aroyl, or lower alkoxycarbonyl; R⁶ is hydrogen, lower alkyl, lower alkoxy, chlorine, bromine, lower alkanoylamino, lower alkoxycarbonylamino, or ##STR33## R⁸ is lower alkyl; lower alkyl substituted with hydroxy, lower alkoxy, cyano, carbamoyl, lower alkylcarbamoyl, lower dialkylcarbamoyl, lower alkanoylamino, lower alkoxycarbonylamino, lower alkanoyloxy, or lower alkoxycarbonyl; or cyclohexyl; and R¹¹ and R¹² are hydrogen or methyl.
 14. A compound according to claim 13 whereinR⁶ is hydrogen, methyl, lower alkanoylamino or lower alkoxycarbonylamino; and R⁸ is lower alkyl, hydroxyethyl, hydroxypropyl, lower alkanoyloxyethyl, lower alkanoyloxypropyl, carbamoylethyl, lower alkylcarbamoylethyl, lower alkanoylaminoethyl, lower alkanoylaminopropyl, lower alkoxycarbonylaminoethyl or lower alkoxycarbonylaminopropyl.
 15. A compound according to claim 1 having the formula ##STR34##
 16. A compound according to claim 1 having the formula ##STR35##
 17. A compound according to claim 1 having the formula ##STR36##
 18. A compound according to claim 1 having the formula ##STR37## wherein R¹ is lower alkoxycarbonyl, carbamoyl, or lower alkylcarbamoyl;R² is hydrogen, lower alkyl, or aryl; R³ is aryl; lower alkanoyl; benzoyl and benzoyl substituted with lower alkyl or lower alkoxy of 1-6 carbons, chlorine and bromine; or lower alkoxycarbonyl; and R⁸ is lower alkyl; lower alkyl substituted with hydroxy, lower alkoxy, cyano, carbamoyl, lower alkylcarbamoyl, lower dialkylcarbamoyl, lower alkanoylamino, lower alkoxycarbonylamino, lower alkanoyloxy, or lower alkoxycarbonyl; or cyclohexyl. 